Light-sensitive silver halide photographic materials

ABSTRACT

A METHOD OF PREVENTING FOG DURING RAPID DEVELOPMENT OF A LIGHT-SENSITIVE SILVER HALIDE EMULSION AT ELEVATED TEMPERATURES BY DEVELOPING SAID EMULSION IN THE PRESENCE OF 4-HYDROXY-6-METHYL-1,3,3A,7-TETRAZAINDENE AND AT LEAST ONE OF A PARTICULAR GROUP OF QUATERNARY AMMONIUM COMPOUNDS.

United States Patent US. Cl. 9650'R 3 Claims ABSTRACT OF THE DISCLOSURE A method of preventing fog during rapid development of a light-sensitive silver halide emulsion at elevated temperatures by developing said emulsion in the presence of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and at least one of a particular group of quaternary ammonium compounds.

The present invention relates to a light-sensitive silver halide photographic material in which a compound represented by the general formula shown later is used as an antifoggant in combination with 4 hydroxy 6 methyl- 1,3,3a,7-tetrazaindene. An object of the present invention is to provide a light-sensitive silver halide photographic material having excellent antifogging properties, particularly one which, even when subjected to quick development treatment, has excellent antifogging properties and has less variation of photographic properties as compared with the case of ordinary development treatment.

Recently, light-sensitive photographic materials have been desired which can be developed quickly by treatment at high temperature in a short period of time. When treated at high temperature, however, light-sensitive photographic materials tend to be increased in fog and are deteriorated in photographic properties, in general.

Light-sensitive photographic materials have heretofore been sensitized by such sensitization methods as sulfur sensitization, reduction sensitization, noble metal sensitization, and sensitization using polyalkylene glycols. Since these methods are liable to degrade the photographic emulsions in antifogging characteristic, in general, there have been used many kinds of antifoggants. Typical examples of such antifoggants are 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 1-phenyl-S-mercaptotetrazole. The former compound acts to stabilize the fog of a silver halide photographic emulsion which is under storage and is relatively low in fog-inhibitin effect on a photographic emulsion immediately after its preparation. On the other hand, the latter compound is high in fog-inhibiting effect on a photographic emulsion immediately after its preparation. Ordinarily, therefore, these two compounds are used together to attain the fog-inhibiting effect. However, the 4-hydroxy- 6-methyl-l,3,3a,7-tetrazaindene is lessened in fog-inhibiting effect during high temperature development, While the 1-phenyl-S-mercaptotetrazole is strong in desensitizing action, and when it has been incorporated in a photographic emulsion in an amount sufficient to inhibit the fog formation at the time of high temperature development, the photographic emulsion is greatly desensitized and is not practical. Accordingly, in the case of the conventional light-sensitive photographic emulsion containing the said antifoggants, the degradation of photographic properties during high temperature development is greater than during ordinary development treatment, and it is difficult to expect a suflicient fog-inhibiting effect.

CJI

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In view of such actual circumstances as mentioned above, we made studies on light-sensitive silver halide photographic emulsions capable of being successfully developed not only by the quick development treatment but also by the ordinary development treatment. As the result, we have found that a light-sensitive silver halide photographic emulsion, which has been incorporated with at least one of the compounds represented by the general formulas (I), (II), (III) and (IV) set forth below in combination with 4-hydroxy-6-meth'yl-l,3,3u,7-tetrazaindene, is markedly lower in degree of desensitization than in the case of the conventional photographic emulsion, shows a high fog-inhibiting effect not only during ordinary development but also at the time of high temperature treatment, and is extremely less in variation of photographic properties.

(III) wherein R and R are individually an alkyl or hydroxyalkyl group having 1 to 18 carbon atoms; R is an alkyl or hydroxyalkyl group having 1 to 18 carbon atoms or an aryl or aralkyl group; X is an anion; Z is a non-metal group necessary to form the hetero ring together with the N atom; A is an alkyl, alkenyl, alkynyl, aryl or aralkyl group; and B is -(CH CH O(CH OCH or CH COCO.CH where n is a positive integer of 1 to 10.

The compounds represented by the above-mentioned general formulas have heretofore been known as sensitizers, as disclosed in US. Pat. 2,288,226, and scarcely display fog-inhibiting effects. When used in combination with 4hydroxy-6-methyl-1,3,3u,7-tetrazaindene, however, they show excellent fog-inhibiting effects by virtue of interactions with the said compound, as is clear from the examples set forth later.

Processes for synthesizing the compounds represented by the above-mentioned general formulas have already been reported in many references. For example, the proc ess for synthesizing the compounds from pyridines and alkyl dihalides is disclosed in Journal of the American Chemical Society, 18, 988 and Annalen der Chemie, 121, 254; the process for synthesizing quaternary salts from xylene dihalides is disclosed in Berichte, 34, 2089; the process for synthesizing the compounds from alkylamines or pyridines and alkylhalides is disclosed in Industrial and Engineering Chemistry, 45, 1022, Chemical and Engineerin News 30, 1282, and Journal of the American Chemical Society, 68, 753 and 63, 147; and the process for synthesizing the compounds from azoles and alkylene dihalides or alkyl halides is disclosed in US. Pats. 2,425,774 and 2,694,716.

Typical examples of the compounds represented by the aforesaid general formula which are effective for practice of the present invention are as follows:

(1) CH; CH; (2) CH: CuHzu N iaHa1 I 3 Bl oftoi on,

(3) CgHs CgHs (4) CaHs 02H! NOH1C=CH1 NCH2'CH1OH C3H 1C1 CH; 03H: 01

)1 i CtzHzs B1 CnHzaOCH: Cl

(7) CH: CHrCHCHzOH (B) CnHn-N H CaHn-N CH3 I CH3 $0 011 I CEQCHgNqCI C CH CHZCQ: B1

11 12 S CH I CH: @4111, or 0.11 Br u cniocnm-ocnrhv CH3 CH3 CH CH; CH:

\ N-CHzQ-CHP-I? on oalonomon rism-Q-om osoicm (19) CH: (1H3 CH3 CH3 N-CHg-O-CHg-N CH3 C104 104 CH (20) CH: 8 CaHn CH:

N-CHz-C O -C O-CHz-N CH; Br Br CH; (21) rm \III/ H C-O(CHa)r-OCH \III/ Br Br 22 cm om on, /CH:

NCH2CH2;N CH; Br Br CH;

(23) CH CH3 C13 CH3 N-CH: O CHzCHz- S -CH:CH3 0 CHz-N CH; Br Br CH;

In adding to a silver halide photographic emulsion, each of the above-mentioned compounds and 4-hydroxy- 6-methyl-l,3,3a,7-tetrazaindene are brought into the form of, for example, aqueous solutions, alkali solutions or alcohol solutions, either singly or in combination with each other, and are added to the emulsion. The amounts of the 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and the compound represented by the aforesaid general formula which are to be added to the emulsion are, respectively, 0.05 to 6.0 g. and less than 1 g. per g. of the silver halide. Further, these compounds may be incorporated into any one the layers constituting a light-sensitive photographic material, such as the protective layer, inter layer, filter layer or other gelatin-containing layer. In this case also, the amounts of the compounds to be incorporated are preferably within the above-mentioned ranges. In any of the above-mentioned cases, the compounds may be added at an optional stage during the steps for production of light-sensitive photographic material.

Light-sensitive silver halide photographic materials obtained in the above manner are quite stable even when subjected to development treatment at a high temperature for a long period of time, and are best suitable for quick development. Further, the photographic materials have excellent photographic properties also in the case where they have been treated under ordinary development conditions. Moreover, they are less affected by the development conditions and have such characteristics that stable photographic properties can always be attained.

The present invention is illustrated in further detail below with reference to examples.

Example 1 A gelatino-silver halide photographic emulsion containing 60 g. of silver iodobromide, in which the amount of silver iodide was 1.5 mol percent, was subjected, at the time of second ripening, to gold sensitization. After completion of the ripening, the emulsion was equally divided into 5 portions, and one portion was used as a control while the remaining 4 portions were combined with the compounds shown in Table 1. These emulsions were individually coated on a polyester film base and then dried to prepare samples. The thus prepared samples were treated according to the sensitometry method regulated in JIS-K-7604 and measured in fog and relative speed to obtain the results shown in Table 1.

5. The compositions of the developers used were as set forth below and the development conditions were as shown in Table l.

to prepare samples. The thus prepared samples were treated in the same manner as in Example '11 to obtain the results shown in Table 2.

TABLE 2 After development Alter development with developer (I) with developer (II) A t at 40 C. for 30 seconds at 20 C. for 4.5 minutes moun added Relative Relative (mg.) Fog speed Fog speed Control 0. 28 100 0. O8 81 750 0. 20 91 0. 06 80 3g 0.09 51 0.06 48 723 0. 25 90 0. 09 83 Compound (1)... 35 87 06 80 gompound (6)... 728 0. 82 0. 09 83 Exemplified 0051566567651: 40 i W 85 81 gxemplifieidgpmpound (l7) 7E3 0. 23 85 0. 07 81 ompoun Exemplified Compound (17).. 75 06 81 06 79 Developer '(1) I G. pound-s -(A) and (B) are the same as in Example '1. Sodium s.ulfite 70 From the above table, it is understood that the samples i 10 according to the present invention have excellent photo- Bortc anhydnde 1 25 graphic properties, and that both in the quick develop- Sodlum carbonate ({nOHOhYdratC) 20 ment treatment and in the ordinary development treati ment, they are free from decrease in sensitivity, show Sodlum hydroxlfie 5 favorable fog-inhibiting efiec'ts and are less in variation s'Methyl'benzlmflzole of photographic properties. Potassium bromide 5 Whatis claimed is: v Glutgralqehyde blsumte 15 l. A method of preventing fog during rapid develop- Aceuc acid 8 ment at elevated temperatures of a light-sensitive silver Wamto make 1 halide emulsion in a photographic material which com- Developer 1:1) prises developing said emulsion in the presence of (A) 4-hydroxy6 methyl 1,3,3a,7 tetr-azaindene and (B) at Metal least one of the compounds represented by either of the Anhydrous sodium sulfite 60 following formulas Hydroquinone 9.0 R1 R1 R2 Sodium carbonate (monohydrate) 53 1 and Z Potassium bromide 4.0 Water to make 1 liter. a X X TABLE 1 After development After development with developer (I) In the table, the developers (I) and ('II) and the comwith developer (II) at 40 C. for 30 seconds at 20 C. for 4.5 minutes Amount added Relative Relative 8-) Fog speed Fog speed Control 0. 31 100 0. 08 82 Compound (A) 750 0. 25 97 0.07 80 gxemplifieidiompound (2 728 0. 21 70 0.09 83 ompoun gxemplifieidgpmpound (21).. 728 1' 08 72 75 ompoun Compound (B) so 06 48 05 41 In the table, the compound '(A) is 4-hydroxy-6-methyl- 1,3,3a,7-tetrazaindene; and the compound \(B) is 1- phenyl-S-mercaptotetrazole.

The same emulsion as in Example 1 was equally divided into 9 portions, and one portion was used as a control while the remaining 8 portions were combined with the antifoggants as shown in Table 2. These emulsions were individually coated on a polyester film base and then dried wherein R and R are individually an alkyl or hydroxyalkyl group having 1 to 18 carbon atoms; R is an alkyl or hydroxyalkyl group having 1 to 18 carbon atoms or a substituted or unsubstituted aryl or araikyl group; X is an anion; Z is a non-metal group necessary to form a pyridine, quinoline or benzothiazole ring by bonding to the N atom; A is an alkyl, alkenyl, alkynyl, aryl or aralkyl group; and B is ((CH -CH O'(CH OCH Where n is a positive integer of l to 10, and wherein said compounds (A) and B) are incorporated in said photographic material.

7 2. A method for developing a light-sensitive silver halide photographic material comprising 4-hydroxy-6- methyl-1,3,3a, 7-tetrazaindene and at least one of the compound-s represented by any of the following general formulas ('I), ('II),'(1II) and IV):

(III) wherein R and (R are individually an alkyl or hydroxyalkyl group having .'1 to 18 carbon atoms; R is an alkyl or hydroxyalkyl group having 1 to 18 carbon atoms or a substituted or unsubstituted aryl or aralkyl group; X is an anion; Z is a non-metal group necessary to form the hetero ring by bonding to the N atom; A is an alkyl, alkenyl, alkynyl, aryl or aralkyl group; and B is -(OH -CH (CH OCH Ame-07011.

References Cited UNITED STATES PATENTS 2,886,437 5/1959 Piper 96-66 R 2,940,851 6/1960 Beavers et al. 96'66.3

2,944,902 7/1960 Carroll et al 96- 107 3,576,633 4/ 1 971 Henn et a1 96- 665 FOREIGN PATENTS 593,4 l1 3/l1960 Canada 96-663 OTHER REFERENCES Accelerated Processing, Photo Methods for Industry,

February 1959, pp. 82-35, 72-73, esp. p. 33.

RON A'Ll) H. SMITH, Primary Examiner M. F. KELIJEY, Assistant Examiner US. Cl. X:R. 9648 QP, 95, 109 

